Anthraquinone dyestuffs



AN'QUINONE DYESTUFFS Milton L. Hoefie, Roseville, Mich and David I.Randall, Easton, Pa., assignors to General Aniline & Film Corporation,New York, N. Y., a corporation of Delaware No Drawing. ApplicationAugust 4, 1954 Serial No. 447,884

9 Claims. (Cl. 260--373) This invention relates tothe production of anew series of anthraquinone dyestutis and more particularly tonnsulfonated compounds having the following general formula:

B O OH R A B1 wherein one R is OH and the other R is CHZOHgX R: Ris-selected from the group consisting of CHZOHQX R2 and R is selectedfrom the group consisting of lower alkyl and CH CH X, X is selected fromthe group consisting of -OH, -CN and -CONH and Y is asubstantivity-increasing radical.

The problem of providing acid gas resistant dyestuffs in the blue rangefor cellulose acetate rayon fibers and other fibrous material having abasis of polymeric material has long been recognized. Other propertieshighly desirable in such dyestuffs include fastness to light and towashing in addition to good substantivity for the fiber. It has beenfound that dyestuffs of the above formula provide a series of blueshaded colors on film, fibrous and other material which havesurprisingly good light-, Wash-, and acid gas fastness properties and agood sub stantivity for the material to be colored. In addition tocellulose acetate, the dyestuffs of this invention may be employed forcoloring other natural and synthetic polymeric material in bulk, film orfiber form, including polyamides, polyesters and polyacrylonitriles andthe like, such as nylon, Orlon, Dacron, Acrilan, Dynel and the like.

In the formula given above, the substantivity-increasing radical Y ispreferably hydroxyalkyl such as hydroxy methyl, hydroxy ethyl and thelike, acidylamino such as acetamido, N-methyl acetamido, and the like,or sulfonarm'do, i. e., SO ND D wherein D and D may be hydrogen, alkyl,hydroxyalkyl, hydroxy alkoxy alkyl, hydroxy polyalkoxy alkyl,cyanoalkyl, and, when taken together, part of a 5 to 7 memberedheterocyclic ring, the alkyl groups having from 1 to 3 carbon atoms, e.g. methyL, ethyl, propyl or isopropyl. However, otherlsubstantivitydncreasing radicals may be employed, as for example,hydroxy ethoxy, hydroxyethoxy ethyl, hydroxyethoxy methyl, hydroxypolyethoxy ethyl, and the like. R may, in addition to being CH CH X, bemethyl, ethyl, propyl, isopropyl, or the like. The preferred compoundsof this invention are those wherein R is an aryl amino radicalcontaining a substantivity-increasing radical and X is CN or -CONH Insuch compounds, at sulfamyl substantivity-increasing radical has beenfound to give greatly improved results.

The dyestuffs of this invention may be readily prepared in diversemanner by condensation of the proper components, if desired in thepresence of catalysts and acid binding agents and in an inert inorganicor organic solvent or diluent such as o-dichlorobenzene, quinoline,pyridine or the like. For example, the nitro groups in4,8-dinitroanthrarufin or 4,5-dinitrochrysazine or a mixture of thesetwo compounds may be selectively replaced, one nitro being replaced bytreatment with two molar equivalents of an appropriately substitutedarylamine of the formula:

followed by replacement of the second nitro group by reaction with twomolar equivalents of an appropriately substituted secondary amine of theformula CHzOHgX wherein R X and Y have the values given above. Inanother modification, both nitro groups in the said dinitroanthrarufinand/ or dinitrochrysazine may be replaced by treatment with anappropriately substituted secondary amine of the above depicted formulato produce dyestuffs having excellent gas fastness properties oncellulose acetate rayon and good substantivity to Dacron and the like.Alternatively, the desired dyestufis may be prepared by condensing theappropriate substituted arylamine and/or secondary amine of theabove-depicted formulae with anthrarufin and/or chrysazine containingother negative radicals in the free alpha positions such as halogen, orthe like by the methods usually employed in the preparation ofarylaminoand alkylamino anthraquinones. In still another modification,an anthraquinone in an intermediate stage of condensation may beemployed as for example l-hydroxyanthraquinone containing a properlysubstituted arylamino group in the 4-position and hydroxy and nitrogroups in the 5- and 8-position. Replacement of the nitro group in suchan intermediate condensation product by reaction With an appropriatelysubstituted secondary amine of the abovedepicted formula will yield thedesired dyestufis of this invention.

The following examples, in which parts are by Weight unless otherwiseindicated, will serve to illustrate the invention, but they are notintended to limit it thereto.

Example 1 Into a reaction vessel equipped With a thermometer, stirrerand reflux condenser were charged 6.0 parts p (4, 8 dihydroxy nitro lanthraquinonyl) N- methylacetanilide, 6.0 partsfifl-iminodipropionitrileand 45 parts o-dichlorobenzene. The reactionmixture was heated at reflux(168170 C.) for six hours. The reaction mixturewas then steam distilled,and the solid product was removed by filtration and washed with hotwater. The product was oven dried and weighed 6.1 parts. This productdyed acetate rayon in red-blue shades of excellent gas fastness.

Example 2 (ONGHzOHmN Into a reaction flask equipped with stirrer,condenser and thermometer were charged 4.4 parts N -(4,8-dihydroxy 5nitro l anthraquinonyl) N bis(2 hydroxyethyl)-rnetanilamide, 6.0 partsB,B'-iminodipropionitrile, 40 parts oedichlorobenzene. The reactionmixture was heated at reflux for six hours, then steam distilled. Thesolid product was removed by filtration and'dried in an oven, yielding3.2-parts of product which dyed acetate rayon in blue shades whichproved to be exceptionally fast to the action of combustion gas fumes.

Example 3 O H IO 0 H OH O OH C CHnCHaGN 3 and CH3 omomoN cH-N 0 OH or.

o H NHQlF-(iLCB;

Into a reaction flask equipped with stirrer, thermometer and refluxcondenser were charged 4.0 parts-condensation product ofp-amino-N-methylacetanilide and a mixture of 4,5-dinitrochrysazine and4,8-dinitro anthrarufin, 8.0 parts B-isopropylaminopropionitrile, and40.0 parts o-dichlorobenzene. The reaction mixture was heated at refluxfor eight hours. It was then steam distilled, and the solid was removedby filtration and washed with warm water. The product was dried-.in anoven and weighed,3.1 parts. This product-.zdyegl acetate rayon in blueshadm possessing :excellent :igassiastness.

Example 5 OH O OH The procedure of Example 4 was repeated except thatthe B-isopropylaminopropionitrile was replacedb? 610 partsB-methylaminopropionitrile. The resulting product dyed acetate rayon inblueshades which possessed excellent gas fastness.

Example 6 CHz'O H20 N (CHahCH-ITT (I? v S 0 1N'(G:HIOH)1 Into a reactionvessel equipped with a stirrer,'-thermometer and reflux condenser werecharged 3.0mm

N (4,8 dihydroxy-S-nitro-l-anthraquinonyl)-N'-bis(2-hydroxyethyDmetanilamide, 6.0 parts fl-isopropylaminopropiom'trile and40 parts o-dichlorobenzene. The'revaction mixture was heated at refluxfor eighthours. The

solvent was then removed by steam distillationg -The product was removedby filtration and washed gwith-hot water and then dried in an oven,yielding -3.0-parts. This product dyed acetate rayon in blueshades-Which possessed excellent gas fastness.

Example 7 GHaCHzGN O O OH S0:N(C: 40 )s The procedure of Ex p 6 wasepeatediexsen ha parts fi-methylaminopropionitrile to yield 2.6 parts ofa product which dyed rayon acetate in deep blue shades which possessedexcellent gas fastness.

Example 8 0H 0 OH O t: N NE N CH: HOCHgC a CHzCHgOH Hz and HOCHzCH:OHICHOH O H A cm Example 9 H0 0 N(CH3CH1CN)2 Into a reaction vesselequipped with a stirrer, thermometer and condenser was charged 6.6 partsdinitIoanthrarufin, 11.0 parts N-N-iminodipropionitrile, 8.0 partsdimethylaniline and 40 parts o-dichlorobenzene. This reaction mixturewas heated at reflux for sixteen hours, and it was then steam distilledand the product was removed by filtration. The product was thensuspended in 750 parts water containing 4 parts sodium carbonate and 4parts sodium bicarbonate. This mixture was stirred at 90-95 C. forthirty minutes and then filtered hot. The product was then oven dried,yielding 6.5 pans which dyed acetate rayon in red-blue shades whichpossessed excellent light and gas fastness.

Example 10 920131 CHzCHgCN CHnCHzCN Into a reaction vessel equipped witha stirrer, condenser and thermometer was charged 4.0 parts4,8-dinitroanthrarufin, 8.0 parts ,B-isopropylaminopropionitrile Example11 CHzOHaCN N ONGHzOHz CHa The procedure of Example 10 was repeatedexcept that the isopropylaminopropionitrile was replaced by 8.0 partsB-methylaminopropionitrile and the reaction mixture was heated at refluxfor fifteen hours. This reaction mixture was worked up as in thepreceding example yielding a product which dyed acetate rayon inred-blue shades of good light and gas fastness.

This invention has been described with respect to several preferredembodiments thereof and various modifications and variations thereofwill become obvious to the person skilled in the art. It is to beunderstood that such modifications and variations are included withinthe spirit and purview of this application and the scope of the appendedclaims.

We claim:

1. An unsulfonated compound of the formula wherein one R is OH and theother R is i R is O OH

1. AN UNSULFONATED COMPOUND OF THE FORMULA